Halosulfonyl sulfooxonium compounds

ABSTRACT

Polyhaloaralkyl (halosulfonyl) sulfooxonium inner salts are prepared by the reaction of benzal halides with sulfur trioxide. The oxonium salts are readily hydrolyzed to afford aldehydes useful in the production of flame retardant polymers. The aldehyde products of oxonium salt hydrolysis may be oxidized to the corresponding carboxylic acid derivatives which are useful pesticides.

Ulllifll States Patent 11 1 1111 3,869,491 Mark et a]. Mar. 4, 1975 [54] HALOSULFONYL SULFOOXONIUM 3,300,515 H1967 Baird et a]. 260/458 X COMPOUNDS FOREIGN PATENTS OR APPLICATIONS 1 lnvemorsl Victor Mark; Carol Mark, both 1,135,120 11/1968 Great Britain 260/599 of Ransomville, NY.

[73] Assignee: Hooker Chemicals & Plastics C0rp., Primary Examiner Leon-Zitver Niagara Falls, NY. Assistant E.\'aminer-Norman Morgenstern Attorney, Agent, or Firm-Peter F. Casella; Donald C. [22] 1971 Studley; William J. Crossetta, Jr. [21] Appl. No.: 123,015

[57] ABSTRACT [52] US. Cl. 260/457, 260/599 polyhaloaralkyl (halosulfonyl) sulfooxonium inner Il'lt- Cl. Salts are p p the reaction of benzal halides [58] held of Search 260/458 618 with sulfur trioxide. The oxonium salts are readily hy- 260/457 drolyzed to afford aldehydes useful in the production of flame retardant polymers. The aldehyde products of [56] References cued oxonium salt hydrolysis may be oxidized to the corre- UNITED ST S PATENTS sponding carboxylic acid derivatives which are useful 1.931.203 10/1933 Meerwern et al 260/618 D pesticides. 2621,1611 12/1952 ROSS et 61. 260/775 AM 3,146,086 8/1964 121116516116 et 61. 260/599 10 Clam, N0 Drawmgs This invention relates to a novel class of halogenated organic disulfooxonium compounds and to methods-for their synthesis. It relates in particular to geminal bis(- halosulfonyl) and halo(halosulfonyl) oxonium compounds, which are uniquely suitable for the preparation of a variety of halogenated, aldehydic and carboxylic acid containing products which are useful as precursors for halogenated polymers, as flame retardant additives for polymers, and as pesticides.

The new class of compounds may be represented by the following general formula:

Y is selected from the group consisting of X and m and n are integers so selected that their sum is the number of substitutable positions available on the aromatic ring, which, when Ar is benzene is 6, when naphthalene is 8 and when anthracene and phenanthrene is 10.

The aromatic nucleus Ar is intended for the purposes of this disclosure to embrace the ring structures of benzene, naphthalene, anthracene and phenanthrene. Thus Ar is an aromatic hydrocarbon moiety of the benzene series containing from 1 to 4 six membered rings in which each substitutable hydrogen on the ring has been replaced by a halogen.

The new compounds are prepared from compounds of the structure Hal Ar(CHX wherein Ar, Hal, X, m and n are as defined above, using sulfur trioxide, in neat form or in solution, as the sec ond reactantf The following chemical equations illustrate some of these novel chemical reactions:

+l cl CHM-2 [+503 c] CH 0 so c1 OJVZSOZCI ct c1 Cl c1 Br Cl 03S Br Cl c1ZCH 9 E 3 CH @cn 3/803 so Clj V Cl Br C1502 2 :1 Br 2 2 CH g so l (:Hci \so2C cl '0 s (i 2 50 12 $03 o CH I CH 0/ 3 CIZCH CHClz c1 s0 c1 2 C1 c1 c1 c1 ;H 0

cl so c1 Cl 1 can] 035\+ V 2 0 CH O O 9 3 l C10 5 2 c1 c1 CIZCH c1 2 -a',a ,a ,2,4,6-nonachloromesitylene,al ,3 ,5 ,7-

The rather wide scope of these reactions is indicated by the variety of halogenated aromatic substrates which readily undergo these insertion reactions. Derivatives of all four of the common halogens are equally suitable as starting materials if they are substituted on mono-, diand polynuclear aromatic compounds. All of these aromatic nuclei carry one or more side chains consisting of the difluoromethyl, chlorofluoromethyl, dichloromethyl, fluorobromomethyl, chlorobromomethyl and dibromomethyl substituents.

As representatives of the multitude of polyhalo aromatic substrates covered by this invention the following compounds can be cited: a,a-dichloro-2,3,4,5,6- pentafluorotoluene,a,a,2,3,4,5,6-heptachlorotoluene, 2,3,4,5,-pentabromo-a,a-dichlorotoluene, 2,3,4,5,6- pentachloroa,a-difluorotoluene, a,2,3,4,5,6-hexachloro-z-fluorotoluene,a,a,a', a,2,3,5,6-octachlorop-xylene,a,a,a',a,2,4,5,6-octachloro-m-xylene, a,a,a,a,3,4,5,6-octachloro-o-xylene,

so Hal Ar CHX(O/ 3 so x and

so- Hal Ar CH(O/ 3 tetrabromo-a,a,a,a-tetrachloro-2,6-dimethylnaphthalene, a,a,a',a',l,2,3,4,5,6,7,8-dodecachloro-9,l0- dimethyl anthracene, 2,3,4,5-tetrabromo-a,a-dichloroo-iodotoluene.

The sulfur trioxide reactant can be used in neat form or in solution. Liquid, stabilized sulfur trioxide, which as a boiling point of 445C, is the preferred form of this reagent, since it has excellent solvent properties and, due to its low boiling point, any excess of it available at the end of the reaction can readily be recovered by distillation. Solutions of sulfur trioxide, especially in sulfuric acid, known as fuming sulfuric acid or oleum, and in other non-reactive solvents, such as trichlorofluoromethane, trichlorofluoroethane, difluorotetrachloroethane, can also be employed. The reactions are carried out usually at atmospheric pressure, since not much benefit can be derived by decreasing or increasing the pressure during the reaction. For the quantitative recovery of the excess of sulfur trioxide, vacuum can be applied at the end of the reaction in order to reduce the temperature at which the reaction mixture is heated and thus to preserve the product without thermal decomposition. The temperature range in which these reactions are carried out is most often at and above room temperature, usually between and 60C, but it can be both lower and higher than this range, depending mostly on the nature of the dihalospheric pressure is advantageous in order to secure a higher reaction temperature than that realized by the refluxing sulfur trioxide at atmospheric pressure. Higher temperature can also be secured by using fuming sulfuric acid as a reactant, especially in a closed system, whereby up to 150C can be employed without loss of appreciable amounts of S0 The new chemical compounds represent a new class of organosulfur derivatives and display highly characteristic physical and chemical properties. Due to their highly reactive nature, identification and characterization is carried out best via proton nuclear magnetic resonance spectroscopy and it is detailed in the specific examples. A quantitative analysis is feasible based on the quantitative nature of the reaction leading to both their formation and their subsequent hydrolysis to products. It is the latter aspect that renders these com- -pounds of great synthetic value: they are hydrolyzed methyl moiety and the solubility characteristics of the reactant in the sulfur trioxide medium. Thus, with not very soluble reactants the use of higher tharratrnd.

quantitatively to the corresponding aromatic aldehydes by the following stoichiometry:

Since these reactions are quantitative, the inorganic hydrolysis products are determined by appropriate titrations and spectral and gravimetric analyses, and the aromatic aldehydes are analyzed by both spectral and elemental (combustion) analyses.

The often ready availability of the polyhalo starting materials, the facility of the reaction under mild synthetic conditions and the usually quantitative yields render these reactions of unique synthetic value.

The resultant mono-, di-, and polyhaloaromatic aldehydes are useful directly as chemical intermediates and as monomers for the preparation of polymeric systems, such as those with the Schiffbase structure, as well as indirectly after their transformations into the corresponding alcohols and acids and acid chlorides and the numerous, well known derivatives of aromatic aldehydes.

The new aromatic derivatives of sulfur trioxide and the insertion reactions yielding them are shown in the following examples, which are intended solely for purposes of illustration and are not to be construed in any way limiting the scope of this invention.

EXAMPLE 1 Preparation of a,2,3,4,5,6- hexachlorobenzyl)chlorosulfonyl)-sulfooxonium hydroxide inner salt, (A) and of 2,3,4,5,6-pentachlorobenzalbis [(chlorosulfonyl)sulfooxonium] dihydroxide bis [inner salt],

I Cl Cl Cl Cl g /0 SO Cl 0 CHCi +2 so c1 2so 2 3 CH (A) 3 "9 Cl Cl Cl Cl Cl c] 50 /0S0 Ci o- 80 C]. C1 1 To a 500 ml 3-neck, tared flask, provided with stirrer, EXAMPLE 2 thermometer and reflux condenser the end of which was attached to a bubble counter, there was charged 20 Preparation of (P- 240 g (3,0 l f f h li id lf r t i id Wi h phenylenedimethine) tetrakis[(chlorosulfonyl)sulfooxstirring there was added, in small portions, through a On m] etrahydroxide tetrakis [inner salt], (C):

ct ct $0 cm so r 2 0 S026] CIZCH cHct 8 50 6 cH (c) c10 s- 0 \o-so ct I C1 C1 I 2 c1 ct so so wide extension tube attached t0 one Of the necks Of the The procedure of Example 1 was exactly repeated exflask, g 1 mol of p a,a,2,3,4,5,6- cept that 38.2 g 0.1 mole) of a,ot,a,a',2,3,5,6- heptachlorotoluene, mp. 118-1l9C. There was, at ta hl m-p-xylene, mp l24-l26C, was substituted room temperature, an immediate development Ofa red for heptachlorotoluene. There was obtained 100.6 g of color, which persisted during the entire addition period ust rd col red r id e, whose iti Corieof the benzal chloride, which was carried out in about sponds to C H Cl O S The product was hydrolyzed 15 minutes, but faded out gradually as the reaction quantitatively to tetrachloroterephthaladehyde, four progressed. There was no significant tempera u e moles of hydrochloric and eight moles of sulfuric acid, change from room temperature during the addition and 40 as d ib d i E l 9,

no as evolution was observed. The progress of the reactiim was monitored best by nuclear magnetic reso- EXAMPLE 3 nance, run directly on the sulfur trioxide solutions, Preparation of 2,4,5,6-tetrachloro(mwhich showed that the single peak due to the starting phenylenedimethine) tetrakis [(chlorosulfonyl)sulmaterial diminished gradually, giving rise to a new peak fooxonium] tetrahydroxide tetrakislinner salt], (D):

Cl Cl 303 Cl Cl c1 /0S0 Cl CHCl 8 s0 0 5 1 ct! 2 (D) +0-S0 Cl I Ci c1-so -o CH c1 CHCl 0 5 SO Cl at PP as the reaction progressed, to Repeating the procedure of Example 1 with the substiond one at 9.31 ppm. The former nuclear magnetic restution f 382 g f g 2 4 5 6 h] ("lance P 15 due to Produm Whereas the low xylene, mp lO0-l0l, for the heptachlorotoluene refield peak represents compound (B). The gross structure of the latter was confirmed also, by its isolation in neat form after the distillation and stripping of the excess of sulfur trioxide, which yielded 66.6 g of a dark orange brown solid, corresponding to the composition of C HCl O S Confirmation for structure (B), indisulted in the formation of the title compound (D) in quantitative yield (101.2 g). Its structure was confirmed by the quantitative analysis of its hydrolysis products as detailed in Example 10.

cated in the title equation, was obtained by its hydroly- EXAMPLE 4 sis which yielded the theoretical amount of penta- Preparation of 3,4,5,6-tctrachloro(ochlorobenzaldehyde, hydrochloric and sulfuric acids. phcnylencdimethinc) tctrzlkis I(chlorusull'onyl)sulas detailed in Example 7. t'noxouiuml tctruhytlruxitic tctrukis linnel' salt]. (l5).

when the Procedure of Example 1 was repeated the The procedure of Example 1 was repeated with the substitution of32 g f flfl'fl'fi substitution of 2,3,4,5-tetrabromo-a,a,6- xylen p 450 C, for the heptachlofotoluene, trichlorotoluene for the heptachlorotoluene. A nearly the was Obtained 3 p red'brown y p 100-8 g1 quantitative yield ofthe bisoxonium compound was obidentified as the title compound by the stoichiometry of mined its formation as well as by the quantitative elemental analysis of its hydrolysis products, which contained the EXAMPLE 7 theoretical amount of hydrochloric and sulfuric acids. Preparation of pentachlorobenzaldehyde.

Cl Cl Compound (8) EH20 Q at 0 CH0 ZHCl L+H 50 EXA 5 The residue 66.6 g of the sulfur trioxide stripping of Expreparation of 2,4,64rich10r0 ample l was added with good stirring to [000 g of icephenyltris(methine)] hexakis [(chlorosulfonyl)sul- Water and the resultant light, cream color precipitate fooxonium] hexahydmxide hexakis [inner salt], (F), was filtered, washed thoroughly with water until it be- 3 C10 so o-so c1 2 cum 2 cH Cl (:1 s03" c1 c1 i 3 C10 5 cu cH 0-so ct (F ct cn cuci 0 s 0 0 c1 3 I so ci so ct The procedure of Example 1 was repeated, except that came essentially acid free and was dried in air. Since 43.0 g (0.1 mole) of a,a,a,a,a",a",2,4,6- the weight of the product after two days at room temnonachloromesitylene, mp 178l80C, was substiperature was slightly more (29.4 g) than the theoretituted for the heptachlorotoluene. The title compound, cal, (27.8 g) it was refluxed with benzene and the water (F) was obtained quantitatively, in 139 g of yield, after was removed azeotropically. There was obtained 1.5 g the excess of sulfur trioxide was eliminated, and was of water.- The benzene solution, which contained a hydrolyzed in high yield to the corresponding trialde- Small amount Of a brown, flocculent material was h d as d ib d i E l 11, treated with charcoal, filtered and stripped, leaving behind 27.5 g of the pure aldehyde, mp l98-200C. Its

EXA 6 purity and identity was confirmed by mixed melting Preparation of 2,3,4,5-tetrabromo-6-chlorobenzalbis P (undepressed) with an authentic Sample p [(chlorosulfonyl)sulfooxonium] dihydroxide bis [inner scoPlcally and by elemental analysis- Its nuclear saltL netic resonancespectrum displayed the single aldehy- 50 Br Cl Br Cl "o SO CI (G) r CHCl i so B CH 2 3 \0 so cl 1 Br Br Br dic proton at 10.28 ppm in deuteriochloroform solu- Repeating the procedure of Example 7 with compound tion, (at 10.22 ppm in dimethylsulfoxide solution, and (D) resulted in h q n it ive f rm la ion of ppm. at 9.60 ppm in deuteriobenzene solution) and its infratitle compound, mp 197C, whose nuclear magnetic red spectrum, run in perchloroethylene and carbon dire onan spec rum hw6d a Singlet at 0.36 pm. sulfide solution, featured maxima at 3395, 2950, 1720, 5 EXAMPLE 11 1528, 1364, 1348, 1310, 1232, 1218, 1190, 1128, 947, 790, 692, 677, 659 and 522 cm. Preparation of calculated f r c,Hc 0; c, 3010; 0,3 31, 2,4,6-trichlorobenzene-1,3,5-tricarboxaldehyde. 63.69%. .1 '5

CH0 Cl Cl Compound (F) 15H 0 6HC1 l2H SOh OCH, 0

Found: C, 30.0; H, 0.3; CI, 63.5%. Repeating the procedure of Example 7 with the substi- Analysis of the inorganic coproducts was carried out tution of compound (F) for compound (B) yielded the by titrimetric and gravimetric determinations on the title compound, mp l84186C, in 90% conversion. lts aqueous phase, The presence of0,2 mole of hydrochlonuclear magnetic resonance spectrum, run in deuterioric acid and 0.4 mole of sulfuric acid was established in chloroform solution, was a singlet at 10.39 ppm and its the water extracts of the aldehyde. infrared spectrum displayed maxima at 3420, 2890, 1725, 1550, 1252, 1172, 993, 958, 720, 540, 520 and EXAMPLE 3 464 cm, obtained as a mull in mineral oil Calculated for C H Cl- O C, 40.90; H, l 1' Cl,

Preparation of 40.1%. i

2,3,4,5-tetrabromo-6-chlorobenzaldehyde. un 9 83 39.0%

. Br Cl Compound (6) 511 fi Br c110 2HC1 411 50,

Br Br When the procedure of Example 7 was repeated with What is claimed is: compound (G) in place of (B) there was obtained an 1. A compound of the formula essentially quantitative yield of the title compound. V 0

EXAMPLE 9 i 3 37 Preparation of tetrachloroterephthalaldehyde. 2 n

Compound (C) l0H O CHO tHCl 8H S0 The procedure of Example 7 was repeated with comwherein Ar is benzene, Hal is independently selected pound (C) instead of(B). There was obtained aquantifrom the group consisting of fluorine, chlorine, brotative yield of the title compound, mp 193C. lts numine and iodine, n is an integer selected from the group clear magnetic resonance spectrum consisted of a sinconsisting of l, 2 and 3 and m+n is 6.

gle peak at 10.34 ppm in deuteriochloroform solution 2. The compound of claim 1 of the formula and its infrared spectrum featured maxima at 2850,

1720, 1340, 1147, 977, 840, 724, 695, 615, 604 and C1 C1 488 cm", run in Nujol mull. c] 802C] 0 i CH EXAMPLE 10 1 121 Preparation of tetrachloroisophthalaldehyde. c] C] S01 Compound (0) 1011 0 C CHO lHCl 811 80,,

OHC

3. The compound of claim 1 of the formula The mp und of claim l of the formula clo s o Cl 3 I 50 S0 Cl Br Cl +I Clo /+CH CH 2 B SO Cl 0-s0c1 r I 2 \0 S0 Cl $03 C Cl I 3 l0 Br Br 30 4. The compound of claim 1 of th e f' ormula C] c] 80 8. A process for making a compound of the formula c1 CH o 3 HaL ArEGHHO 3 c1 s0 -o cu 'cl 2 I 303 no We which comprises reacting sulfur trioxide with a compound of the formula 03S SO Cl Hal,,,Ar(CHX 5. The compound of claim 1 of the formula wherein Ar is an aromatic nucleus selected from the group 3 2 consisting of benzene, naphthalene, anthracene CI 0 so and phenanthrene;

3 Hal is a halogen selected from the group consisting C1 f C] of fluorine, chlorine, bromine and iodine;

2 X is a halogen comprising fluorine, chlorine and bromine; cl 9 2 2 Y is a substituent selected from the group consisting 3 ofX and SO Cl 2 V80 I v 6. The compound of claim 1 of the formula S03- S03- 40 C10 (LS0 C] m and n are integers so selected that their sum is the 2 2 number of substitutable positions available on the aromatic ring, which, when Ar is benzene is 6. 3 c1 C] so when naphthalene is 8 and when anthracene and O 1 3 phenanthrene is 10. C10 5 CH 5 c1 9. The process of claim 8 wherein an excess of neat,

2 liquid sulfur trioxide lS the reactant.

- 3 o c] 0 10. The process of claim 8 in which the sulfur triox- I ide reactant is employed in a diluent selected from the $0 61 3 302C] 0 group consisting offl sulf kurici acid and a perhaloalkane. 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 of the formula
 3. The compound of claim 1 of the formula
 4. The compound of claim 1 of the formula
 5. The compound of claim 1 of the formula
 6. The compound of claim 1 of the formula
 7. The compound of claim 1 of the formula
 8. A process for making a compound of the formula
 9. The process of claim 8 wherein an excess of neat, liquid sulfur trioxide is the reactant.
 10. The process of claim 8 in which the sulfur trioxide reactant is employed in a diluent selected from the group consisting of sulfuric acid and a perhaloalkane. 